Nitrilazoturo

Nitrilazoturo (trans)
Struttura di Lewis del nitrilazoturo
Struttura di Lewis del nitrilazoturo
Struttura 3D del nitrilazoturo
Struttura 3D del nitrilazoturo
Struttura 3D van der Waals del nitrilazoturo
Struttura 3D van der Waals del nitrilazoturo
Nome IUPAC
Nitrilazoturo[1]
Abbreviazioni
N4O2
Nomi alternativi
Diossido tetranitrogeno
Caratteristiche generali
Formula bruta o molecolareN4O2
Massa molecolare (u)88,03[2]
Numero CAS40006-84-6 Immagine_3D
PubChem22902439
SMILES
[N-]=[N+]=N[N+]([O-])(=O)
Indicazioni di sicurezza
Frasi H---[3]
Consigli P---[3]

Il nitrilazoturo o diossido di tetranitrogeno è un ossido nitrico instabile di formula chimica N4O2 e può essere considerato sia un composto inorganico con legame covalente tra la porzione di molecola azoturo e il nitrile, sia un composto del nitrile. Il contenuto di azoto nella molecola è del 63,65%.

Evidenze sperimentali

Una prima indicazione della formazione del composto di tetrafluoroborato di nitronio e litioazoturo in acetonitrile o tetracloruro di carbonio a basse temperature fu trovata già nel 1973.[4]

Reazioni di cloruro di nitrile con azidi come l'azoturo trimetilsilile o il titandiciclopentanildiazide diedero invece del nitrilazoturo il composto ClN.[5]

Un altro tentativo di produrre nitrilazoturo è stato quello nella figura appresso della reazione di NaN3 con nitronioesafluoroantimoniato in CO2 liquida a -50 °C sotto pressione, in cui il composto è stato rilevato solo spettroscopicamente e non è mai stato isolato.[5]

Sintesi e proprietà

Il nitrilazoturo gassoso N4O2 viene generato da una reazione eterogenea gassosa di ClNO2 con il preparato AgN3 fresco a −50 °C.

ClNO2(g) + AgN3(s) → N4O2(g) + ClAg

La struttura geometrica ed elettronica della molecola nella fase gassosa è stata caratterizzata in situ dalla PES e da calcoli teorici in chimica quantistica. L'energia di prima ionizzazione sperimentale (prima linea verticale) di N4O2 è di 11,39 eV, corrispondente alla ionizzazione di un elettrone sul più alto orbitale molecolare occupato (HOMO).

Una spaziatura apparente vibrazionale di 1600±60cm−1 sulla seconda banda a 12,52 eV conferma una struttura molecolare stabile energeticamente nella fase gassosa. A completamento dei dati sperimentali, è stato prodotto un plot della superficie potenziale-energia di questa molecola transitoria strutturalmente nuova. Sia i calcoli teorici sia i risultati della spettroscopia suggeriscono una molecola con struttura degli atomi trans-planare, inoltre viene favorita la decomposizione ciclica con 5 atomi transitoria che degenera in 2 molecole di N2O.[6]

Note

  1. ^ (EN) Nomenclature of Inorganic Chemistry : IUPAC Recommendations 2005 (Red Book), Cambridge, The Royal Society of Chemistry, 2005, ISBN 978-0-85404-438-2.
  2. ^ (EN) IUPAC Commission on Isotopic Abundances and Atomic Weights., Atomic weights of the elements 2017, su Queen Mary University of London.
  3. ^ a b Questa sostanza non è stata ancora classificata in termini di pericolosità o una fonte attendibile e stimabile non è stata ancora trovata.
  4. ^ (EN) Doyle, M.P.; Maciejko, J.J.; Busman, S.C., Reaction between azide and nitronium ions, formation and decomposition of nitryl azide, in J. Am. Chem. Soc., n. 95, 1973, pp. 952-953, DOI:10.1021/ja00784a069.
  5. ^ a b (EN) Klapötke, T.M.; Schulz, A.; Tornieporth-Oetting, C., Studies of the Reaction Behavior of Nitryl Compounds Towards Azides: Evidence for Tetranitrogen Dioxide, N4O2, in Chem. Ber., n. 127, 1994, pp. 2181-2185, DOI:10.1002/cber.1491271115.
  6. ^ (EN) Zeng, Xiaoqing; Ge, Maofa; Sun, Zheng; Bian, Jiang; Wang, Dianxun, Gaseous nitryl azide N4O2: A joint theoretical and experimental study, in Journal of Molecular Structure, vol. 840, n. 1-3, Elsevier, 09/2007, pp. 59-65, DOI:10.1016/j.molstruc.2006.11.034.

Bibliografia

Altri progetti

  Portale Chimica: il portale della scienza della composizione, delle proprietà e delle trasformazioni della materia

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